Method of stabilization of a haloolefin-based composition

ABSTRACT

The present invention relates to a haloolefin-based composition comprising a haloolefin and water and being used for at least one application selected from the group consisting of heat transfer media, refrigerants, foaming agents, solvents, cleaning agents, propellants, and fire extinguishers. The haloolefin-based composition comprising a haloolefin and water is used for at least one application selected from the group consisting of heat transfer media, refrigerants, foaming agents, solvents, cleaning agents, propellants, and fire extinguishers.

TECHNICAL FIELD

The present invention relates to a haloolefin-based composition and usethereof.

BACKGROUND ART

Hydrofluorocarbons (HFCs), such as HFC-125 and HFC-32, have been widelyused as important substitutes for CFCs, HCFCs, etc., which are known assubstances that deplete the ozone layer. Known examples of suchsubstitutes include “HFC-410A,” which is a mixture of HFC-32 andHFC-125, “HFC-404A,” which is a mixture of HFC-125, HFC-134a, andHFC-143a, etc.

Such substitutes have various applications, such as heat transfer media,refrigerants, foaming agents, solvents, cleaning agents, propellants,and fire extinguishers, and are consumed in large amounts. However,since these substances have a global warning potential (GWP) severalthousand times higher than that of CO₂, many people are concerned thattheir diffusion may affect global warming. As a global warmingcountermeasure, the substances are collected after being used; however,not all of them can be collected, and their diffusion due to leakage,etc., cannot be disregarded. For use in refrigerants, heat transfermedia, etc., although substitution with CO₂ or hydrocarbon-basedsubstances has been studied, CO₂ refrigerants have many difficulties inreducing comprehensive greenhouse gas emissions, including energyconsumption, because of the requirement of large equipment due to thelow efficiency of the CO₂ refrigerants. Hydrocarbon-based substancesalso pose safety problems due to their high flammability.

Hydrofluoroolefins with a low warming potential are recently attractingattention as substances that can solve these problems. Hydrofluoroolefinis a generic name for unsaturated hydrocarbons containing hydrogen,fluorine, and chlorine, and includes substances represented by thefollowing chemical formulae. The description in parentheses followingeach chemical formula indicates the refrigerant number typically usedfor refrigerant purposes.

CF₃CF═CF₂ (HFO-1216yc or hexafluoropropene),

CF₃CF═CHF (HFO-1225ye),

CF₃CF═CH₂ (HFO-1234yf),

CF₃CH═CHF (HFO-1234ze),

CF₃CH═CH₂ (HFO-1243zf)CF₃CCl═CH₂ (HCFO-1233xf),CF₂ClCCl═CH₂ (HCFO-1232xf),

CF₃CH═CHCl (HCFO-1233zd), CF₃CCl═CHCl (HCFO-1223xd), CClF₂CCl═CHCl(HCFO-1222xd),

CFCl₂CCl ═CH₂ (HCFO-1231xf), andCH₂ClCCl═CCl₂ (HCO-1230xa).

Of these, fluoropropenes are particularly promising substances ascandidates for refrigerants or heat transfer media with a low GWP;however, they may sometimes gradually decompose over time, etc., andthus are not highly stable. Accordingly, these substances have a problemof gradually reducing performance depending on the situation orenvironment when used in various applications.

To enhance the stability of fluoropropenes, a method for adding a phenolcompound to a composition containing HFO-1234yf and CF₃I is known (see,for example, Patent Literature 1).

CITATION LIST Patent Literature

PTL 1: WO2005/103187

SUMMARY OF INVENTION Technical Problem

The above method can improve the stability of HFO-1234yf by the effectof the phenol compound; however, it still has a problem of handlingdifficulty during mixing. The method for improving stability by adding aphenol compound as described above may also reduce the performance offluoropropenes by the effect of the phenol compound, and has a problemin improving stability while maintaining performance.

The present invention was accomplished based on the above, and an objectof the present invention is to provide a haloolefin-based compositioncomprising a highly-stable haloolefin in which decomposition andoxidization are inhibited, and the haloolefin-based composition beingused in a heat transfer medium, refrigerant, foaming agent, solvent,cleaning agent, propellant, or fire extinguisher. Another object of thepresent invention is use of the highly stable haloolefin-basedcomposition in a heat transfer medium, refrigerant, foaming agent,solvent, cleaning agent, propellant, or fire extinguisher.

Solution to Problem

As a result of extensive research to achieve the above object, thepresent inventors found that the above object can be attained by using acomposition containing a haloolefin and water, and accomplished theinvention. Specifically, the present invention relates to the followinghaloolefin-based compositions and use thereof.

1. A haloolefin-based composition comprising a haloolefin and water, thehaloolefin-based composition being used for at least one applicationselected from the group consisting of heat transfer media, refrigerants,foaming agents, solvents, cleaning agents, propellants, and fireextinguishers.2. The composition according to Item 1, wherein the amount of the wateris 200 mass ppm or less based on the total amount of the haloolefin.3. The composition according to Item 1 or 2, which further comprisesoxygen.4. The composition according to Item 3, wherein the amount of the oxygenis 0.35 mol % or less based on the total amount of the haloolefin.5. The composition according to any one of Items 1 to 4, wherein thehaloolefin is tetrafluoropropene.6. The composition according to Item 5, wherein the tetrafluoropropeneis 2,3,3,3-tetrafluoropropene.7. The composition according to Item 5, wherein the tetrafluoropropeneis 1,3,3,3-tetrafluoropropene.8. The composition according to any one of Items 1 to 7, which furthercomprises at least either, or both, of polyalkyleneglycol andpolyolether as a lubricating oil.9. Use of a haloolefin-based composition comprising a haloolefin andwater for at least one application selected from the group consisting ofheat transfer media, refrigerants, foaming agents, solvents, cleaningagents, propellants, and fire extinguishers.10. The use according to Item 9, wherein the amount of the water is 200mass ppm or less based on the total amount of the haloolefin.11. The use according to Item 9 or 10, wherein the composition furthercomprises oxygen.12. The use according to any one of Items 9 to 11, wherein the amount ofthe oxygen is 0.35 mol % or less based on the total amount of thehaloolefin.13. The use according to any one of Items 9 to 12, wherein thehaloolefin is tetrafluoropropene.14. The use according to Item 13, wherein the tetrafluoropropene is2,3,3,3-tetrafluoropropene.15. The use according to Item 13, wherein the tetrafluoropropene is1,3,3,3-tetrafluoropropene.16. The use according to any one of Items 9 to 15, wherein thecomposition comprises at least either, or both, of polyalkyleneglycoland polyolether as a lubricating oil.

Advantageous Effects of Invention

The haloolefin-based composition of the present invention is used for atleast one application selected from the group consisting of heattransfer media, refrigerants, foaming agents, solvents, cleaning agents,propellants, and fire extinguishers, and contains water as an essentialcomponent. Because the composition contains water, the stability ofhaloolefin is improved. Specifically, since the double bond in themolecule of the haloolefin can be stably present, and the haloolefindoes not easily cause oxidization, the performance of the haloolefin isnot likely to be lost for a long period of time. Accordingly, since thecomposition can provide suitable performance as a heat transfer medium,refrigerant, foaming agent, solvent, cleaning agent, propellant, or fireextinguisher, it is suitable for any of these applications.

Further, in the present invention, the haloolefin-based compositioncontaining a haloolefin and water is used as a heat transfer medium,refrigerant, foaming agent, solvent, cleaning agent, propellant, andfire extinguisher. As described above, since the haloolefin in thehaloolefin composition is stable, performance is not likely to reduce.Accordingly, the composition is suitable for any of applications,including a heat transfer medium, refrigerant, foaming agent, solvent,cleaning agent, propellant, and fire extinguisher.

DESCRIPTION OF EMBODIMENTS

Hereinafter, the embodiments of the present invention are explained indetail.

The haloolefin-based composition used for at least one applicationselected from the group consisting of heat transfer media, refrigerants,foaming agents, solvents, cleaning agents, propellants, and fireextinguishers (hereinbelow, referred to as “composition”) comprises atleast haloolefin and water.

Because the composition contains water as an essential component, thedouble bond in the molecule of the haloolefin can be stably present, andoxidization of the haloolefin does not easily occur. As a result, thestability of the haloolefin is improved.

The haloolefin is an unsaturated hydrocarbon having a halogen atom, suchas fluoride or chlorine, as a substituent. In the haloolefin, all of thehydrogen may be substituted with halogen atoms, or part of the hydrogenmay be substituted with halogen atoms. The number of carbon atoms in thehaloolefin is not particularly limited, and it is, for example, 3 to 10.To increase the stability of the haloolefin in the composition, thenumber of carbon atoms in the haloolefin is preferably 3 to 8, andparticularly preferably 3 to 6. The haloolefin contained in thecomposition may be a single compound or a mixture of different two ormore compounds.

Particularly preferable examples of the haloolefin includetetrafluoropropene, pentafluoropropene, and trifluoropropene. The isomertypes of these compounds are not particularly limited. Particularlypreferable examples of the haloolefin include 2,3,3,3-tetrafluoropropene(HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze),1,2,3,3-tetrafluoropropene (HFO-1234ye), 1,1,2,3-tetrafluoropropene(HFO-1234yc), 1,2,3,3,3-pentafluoropropene (HFO-1225ye),1,1,3,3,3-pentafluoropropene (HFO-1225zc), 3,3,3-trifluoropropene(HFO-1243zf), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz),1,1,1,2,4,4,5,5,5-nonafluoropentene (HFO-1429myz), etc.

The haloolefin produced by a known method can be used. One such exampleincludes a method for subjecting fluoroalkane to dehydrofluorination inthe presence of a catalyst (a method described, for example, inJP2012-500182A). The number of carbon atoms of the fluoroalkane is notparticularly limited, and it is preferably 3 to 8, and particularlypreferably 3 to 6. For example, when the haloolefin istetrafluoropropene, pentafluoropropane is used as a starting material,and subjected to dehydrofluorination reaction in the presence of acatalyst to produce tetrafluoropropene. Specifically, when thehaloolefin is 2,3,3,3-tetrafluoropropene (HFO-1234yf),1,1,1,2,3-pentafluoropropane and/or 1,1,1,2,2-pentafluoropropane areused as starting materials, and subjected to dehydrofluorinationreaction in the presence of a catalyst to produce2,3,3,3-tetrafluoropropene (HFO-1234yf). When the haloolefin is1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,1,3,3-pentafluoropropane isused as a starting material, and subjected to dehydrofluorinationreaction in the presence of a catalyst to produce1,3,3,3-tetrafluoropropene (HFO-1234ze).

In the production of haloolefin according to the above method, abyproduct may also be produced in addition to the target haloolefin. Inthis case, the resulting product may be purified to remove the byproductto obtain target 2,3,3,3-tetrafluoropropene with high purity.Alternatively, haloolefin may be obtained in the state containing thebyproduct without performing purification or by reducing the purity ofpurification. For example, when 2,3,3,3-tetrafluoropropene is producedaccording to the above production method, E- and Z-isomers of1,3,3,3-tetrafluoropropene, etc., are produced as byproducts. In thiscase, the byproducts may be removed by purifying the resulting productto obtain the target 2,3,3,3-tetrafluoropropene with high purity, or E-and Z-isomers of 1,3,3,3-tetrafluoropropene may be contained asbyproducts. Accordingly, when the haloolefin is produced bydehydrofluorinating fluoroalkane in the presence of a catalyst, it maycontain a byproduct. In the above production method, chromium catalysts,such as chromium oxide or fluorinated chromium oxide, and other metalcatalysts can be used as catalysts, and the reaction can be performed ata temperature in the range of 200 to 500° C.

The amount of the byproduct is preferably 0.1 mass ppm or more to lessthan 10,000 mass ppm based on the total weight of haloolefin, and thehaloolefin stabilizing effect may not be significantly inhibited whenthe amount of the byproduct is in this range.

Water is not particularly limited, and purified water, such as distilledwater, ion exchange water, filtered water, tap water, and ultrapurewater obtained by a commercially available device for generating purewater, etc., can be used. However, since water containing acid, such asHCl, may corrode equipment or reduce the haloolefin stabilizing effect,it is preferable to remove HCl, etc., to an undetectable level in atypical analysis method. The amount of acid is preferably 10 mass ppm orless, and more preferably 1 mass ppm or less based on the total amountof the haloolefin, water, and byproduct in the composition.

Although the pH of the water is not particularly limited, it isgenerally in the range of 6 to 8. When the amount of acid in the wateris in the above range, the pH of the water is generally within the rangeof 6 to 8.

The amount of water in the composition is preferably 200 mass ppm orless based on the total amount of the haloolefin. In this range, thehaloolefin stabilizing effect is fully exhibited. The amount of waterbeing 200 mass ppm or less, and more preferably less than 30 mass ppmbased on the total amount of haloolefin can easily prevent devicecorrosion and the acceleration of haloolefin decomposition. The lowerlimit of the amount of water in the composition is not limited as longas the effect of the present invention is exhibited. For example, it is0.1 mass ppm, and more preferably 3 mass ppm. When the amount of wateris in this range, the stability of haloolefin in the composition isfurther improved.

The amount of water in the composition is particularly preferably over 3mass ppm and less than 30 mass ppm. In this range, the stability ofhaloolefin in the composition is further improved. The amount of waterin the composition being less than 30 mass ppm inhibits prevention ofrefrigerant performance.

When the byproduct is also produced in the production of haloolefin, theamount of the byproduct in the composition is preferably 0.1 mass ppm ormore to less than 10,000 mass ppm based on the total amount ofhaloolefin. In this range, the haloolefin stabilizing effect can besufficiently exhibited.

The composition may contain other known additives as long as the effectof the present invention is not inhibited. The amount of other additivesis preferably 50 mass % or less, and more preferably 40 mass % or lessbased on the total amount of the composition.

The composition can be prepared by any method. For example, eachcomponent is prepared and mixed in a predetermined composition ratio,thus obtaining a composition.

In the composition, because of the presence of water, the double bond ofhaloolefin is stably present, which is not likely to cause oxidization,attaining highly stable haloolefin. Accordingly, the composition can bestored for a long period of time as compared with typical haloolefins.Moreover, because of the highly stable haloolefin, the performance ofhaloolefin may not be significantly impaired. Accordingly, thecomposition can provide stable performance as a heat transfer medium,refrigerant, foaming agent, solvent, cleaning agent, propellant, or fireextinguisher. Specifically, since decomposition or oxidization ofhaloolefin is not likely to occur, reduced performance in variousapplications is not likely to be reduced, thus, stable performance canbe maintained even after a long period of time. Accordingly, thecomposition can provide excellent functions when used for any of theapplications, including a heat transfer medium, refrigerant, foamingagent, solvent, cleaning agent, propellant, and fire extinguisher.

The composition can further contain oxygen. When the compositioncontains oxygen, the amount of the oxygen is preferably 0.35 mol % orless based on the total amount of the haloolefin. When the amount ofoxygen is in this range, the stability of haloolefin in the compositionis further improved. From this point of view, a lower amount of oxygenin the composition is better. However, as described above, since thecomposition contains water, the stability of the haloolefin can bemaintained by the effect of the water, as long as the amount of oxygenis in the above range. The lower limit of the amount of oxygen in thecomposition is, for example, 1 ppm, which is the detection limit of gaschromatography.

Haloolefin has been used as a heat transfer medium, refrigerant, foamingagent, solvent, cleaning agent, propellant, or fire extinguisher. Sincethe haloolefin in the composition has particularly excellent stability,the composition is especially suitable for any of these applications.

Examples of the haloolefin used as a heat transfer medium, refrigerant,foaming agent, solvent, cleaning agent, propellant, or fire extinguisherinclude 2,3,3,3-tetrafluoropropene (HFO-1234yf),1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,2,3,3-tetrafluoropropene(HFO-1234ye), 1,1,2,3-tetrafluoropropene (HFO-1234yc),1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,3,3,3-pentafluoropropene(HFO-1225zc), 3,3,3-trifluoropropene (HFO-1243zf),1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz),1,1,1,2,4,4,5,5,5-nonafluoropentene (HFO-1429myz), etc.

When the composition is used as a refrigerant or a heat transfer mediumas described above, 2,3,3,3-tetrafluoropropene (HFO-1234yf),1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,2,3,3-tetrafluoropropene(HFO-1234ye), 1,2,3,3,3-pentafluoropropene (HFO-1225ye),3,3,3-trifluoropropene (HFO-1243zf), etc., are particularly advantageousas haloolefins.

When the composition is used as a refrigerant or a heat transfer medium,at least either, or both, of polyalkyleneglycol and polyolether can becontained as a lubricating oil in the composition. In this case, theamount of the lubricating oil is 10 to 50 mass % based on the totalamount of haloolefin, water, and byproduct in the composition; however,it is not particularly limited to this range because it differsdepending on the specification of the freezer oil tank. When the amountof lubricating oil is in this range, the stability of haloolefin is notimpaired. Moreover, the lubricating oil may further contain polyvinylether (PVE), or may be formed of polyvinyl ether alone.

Examples of polyalkyleneglycol (PAG) include “SUNICE P56,” etc.,produced by Japan Sun Oil Company Ltd. Examples of polyolether (POE)include “Ze-GLES RB32,” etc., produced by JX Nippon Oil & EnergyCorporation.

The conventional refrigerant or heat transfer medium that mainlycontains haloolefin is likely to cause decomposition or oxidization whenit is in contact with metal, etc., and is likely to lose performance asa refrigerant or heat transfer medium. However, when the abovecomposition is used as a refrigerant or heat transfer medium, areduction in the performance can be inhibited because of the highstability of the haloolefin.

EXAMPLES

The present invention is explained in detail below with reference to theExamples, but the present invention is not limited to the embodiments ofthe Examples.

Example 1

2,3,3,3-Tetrafluoropropene (hereinbelow simply referred to as“HFO-1234yf”) and water were prepared and mixed to produce three typesof haloolefin-based compositions containing water in amounts of 10 massppm, 200 mass ppm, and 10,000 mass ppm relative to the HFO-1234yf. TheHFO-1234yf was produced, for example, by the method described in Example1 of JP2012-500182A, and JP2009-126803A. HF generated in the aboveproduction was deoxidized by using a water washing column and an alkalicolumn containing an NaOH aqueous solution. The resultinghaloolefin-based composition might contain a byproduct (for example,1,3,3,3-tetrafluoropropene) generated in the production of HFO-1234yf.

Example 2

1,3,3,3-Tetrafluoropropene (hereinbelow simply referred to as“HFO-1234ze”) and water were prepared and mixed to produce three typesof haloolefin-based compositions containing water in amounts of 10 massppm, 200 mass ppm, and 10,000 mass ppm relative to the HFO-1234ze. TheHFO-1234ze was obtained together with HFO-1234yf by thedehydrofluorination of HFC-245eb according to the method described inJP2012-500182. HF generated in the above production was deoxidized byusing a water washing column and an alkali column containing an NaOHaqueous solution.

Comparative Example 1

A haloolefin-based composition was obtained by the same method as inExample 1 except that water was not added.

Comparative Example 2

A haloolefin-based composition was obtained by the same method as inExample 2 except that water was not added.

Haloolefin Stability Test 1

The haloolefin-based compositions obtained in the Examples andComparative Examples were subjected to a haloolefin stability test asdescribed below. The haloolefin-based composition was added in a mannersuch that the amount of haloolefin was 0.01 mol to a glass tube (ID 8 mmΦ×OD 12 mm Φ×L 300 mm), a side of which was sealed. The tube washermitically sealed. The tube was allowed to stand in a constanttemperature bath in a 150° C. atmosphere, and was kept for one week inthis state. Subsequently, the tube was removed from the constanttemperature bath and cooled, and then acid in the gas inside the tubewas analyzed to evaluate the stability of the haloolefin.

Haloolefin Stability Test 2

The haloolefin-based compositions obtained in the Examples andComparative Examples were subjected to a haloolefin stability test asdescribed below. The haloolefin-based composition was added in a mannersuch that the amount of haloolefin was 0.01 mol to a glass tube (ID 8 mmΦ×OD 12 mm Φ×L 300 mm), a side of which was sealed. Subsequently, oxygenwas enclosed in the tube by adjusting. The tube was allowed to stand ina constant temperature bath in a 150° C. atmosphere, and was kept forone week in this state. Subsequently, the tube was removed from theconstant temperature bath and cooled, and then acid in the gas insidethe tube was analyzed to evaluate the stability of the haloolefin.

Acid in the gas was analyzed according to the following method. Gasremaining in the tube after cooling was completely coagulated by usingliquid nitrogen. Subsequently, the tube was opened and graduallydefrosted to collect gas in a sampling bag. 5 g of pure water was pouredinto the sampling bag, and acid was extracted into the pure water whileefficiently bringing the pure water into contact with the collected gas.The extract was detected by ion chromatography, and the amounts (massppm) of fluoride ions (F—) and trifluoroacetate ions (CF3COO⁻) weremeasured.

Table 1 shows the test results. In Table 1, “yf” and “ze (E)”respectively indicate “HFO-1234yf” and “HFO-1234ze”. (E) in “ze (E)”indicates the E isomer of HFO-1234ze.

TABLE 1 Type Amount Amount Example/ of of of Amount of Acid Comparativehalo- oxygen water (mass ppm) No. Example olefin (mol %) (mass ppm) F⁻CF₃COO⁻ 1 Comparative yf 0 0 (N.D.) <1 <1 Example 1 2 Example 1 0 10 <1<1 3 Example 1 0 200 <1 <1 4 Example 1 0 10000 <1 <1 5 Comparative 0.0100 (N.D.) 70 550 Example 1 6 Example 1 0.010 10 35 90 7 Example 1 0.010200 10 25 8 Example 1 0.010 10000 <1 10 9 Comparative 0.115 0 (N.D.) 3001850 Example 1 10 Example 1 0.115 10 100 330 11 Example 1 0.115 200 30100 12 Example 1 0.115 10000 3 20 13 Comparative 0.345 0 (N.D.) 10055850 Example 1 14 Example 1 0.345 10 330 1900 15 Example 1 0.345 200 110675 16 Example 1 0.345 10000 50 275 17 Comparative Ze (E) 0 0 (N.D.) <1<1 Example 2 18 Example 2 0 10 <1 <1 19 Example 2 0 200 <1 <1 20 Example2 0 10000 <1 <1 21 Comparative 0.010 0 (N.D.) 80 610 Example 2 22Example 2 0.010 10 30 95 23 Example 2 0.010 200 15 40 24 Example 2 0.01010000 3 20 25 Comparative 0.115 0 (N.D.) 410 1900 Example 2 26 Example 20.115 10 105 385 27 Example 2 0.115 200 50 120 28 Example 2 0.115 1000010 45 29 Comparative 0.345 0 (N.D.) 1100 6020 Example 2 30 Example 20.345 10 335 1930 31 Example 2 0.345 200 130 700 32 Example 2 0.34510000 55 290

The amount of oxygen in each of composition Nos. 5 to 8 in Table 1 wasset to 0.010 mol %. Since composition No. 5 did not contain water, theamount of acid in composition No. 5 was larger than those of compositionNos. 6 to 8 containing water. This indicates that since the amount ofacid in composition No. 5 was larger, the decomposition or oxidizationof HFO-1234yf, which was a haloolefin, advanced as compared tocomposition Nos. 6 to 8. The results indicate that HFO-1234yf, which wasa haloolefin, was stabilized in the compositions containing water. Theamount of oxygen in each of composition Nos. 9 to 12 was 0.115 mol %,and the amount of oxygen in each of composition Nos. 13 to 16 was 0.345mol %; however, the results of composition Nos. 13 to 16 showed asimilar tendency to the results obtained when the amount of oxygen addedwas 0.115 mol %. Further, when the haloolefin was HFO-1234ze (Nos. 21 to24, 25 to 28, and 29 to 32), a similar tendency was observed. Incomposition Nos. 1 to 4 and 17 to 20, the amount of acid was below 1mass ppm, and it was found that most of the haloolefin decomposition didnot proceed. This was presumably because oxygen was not added to thesystem, causing no oxidization, etc. Accordingly, in the systemcontaining substantially no oxygen, the haloolefin was always stableregardless of whether water was contained in the composition.

The above clearly indicates that water contained in the compositionstabilizes haloolefin as in the present invention. This indicates thatthe composition can provide excellent performance as a heat transfermedium, refrigerant, foaming agent, solvent, cleaning agent, propellant,or fire extinguisher, and the performance can be stably maintained.Accordingly, the composition is suitable for any of the applications,including a heat transfer medium, refrigerant, foaming agent, solvent,cleaning agent, propellant, and fire extinguisher.

1-14. (canceled)
 15. A method of stabilization of a haloolefin-basedcomposition, comprising combining a haloolefin, oxygen and water in ahaloolefin-based composition, wherein the amount of the oxygen is morethan 0 mol %, and 0.35 mol % or less, based on the total amount of thehaloolefin, the amount of the water is 3 ppm by weight or more and 200ppm by weight or less, based on the total amount of the haloolefin, andwherein the haloolefin comprises 2,3,3,3-tetrafluoropropene and1,3,3,3-tetrafluoropropene, and the amount of the2,3,3,3-tetrafluoropropene is 0.1 to 10000 ppm by weight based on thetotal amount of the haloolefin.
 16. The method according to claim 1,further comprising combining at least one lubricating oil selected fromthe group consisting of a polyalkyleneglycol and a polyolester in thehaloolefin-based composition.